WO2006046312A1 - Papier pour impression à jet d’encre - Google Patents

Papier pour impression à jet d’encre Download PDF

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Publication number
WO2006046312A1
WO2006046312A1 PCT/JP2004/016375 JP2004016375W WO2006046312A1 WO 2006046312 A1 WO2006046312 A1 WO 2006046312A1 JP 2004016375 W JP2004016375 W JP 2004016375W WO 2006046312 A1 WO2006046312 A1 WO 2006046312A1
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WO
WIPO (PCT)
Prior art keywords
water
ink
polyvalent metal
recording paper
metal compound
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Application number
PCT/JP2004/016375
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English (en)
Japanese (ja)
Inventor
Toshihiko Iwasaki
Keiji Ohbayashi
Original Assignee
Konica Minolta Photo Imaging, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Photo Imaging, Inc. filed Critical Konica Minolta Photo Imaging, Inc.
Priority to PCT/JP2004/016375 priority Critical patent/WO2006046312A1/fr
Priority to EP05107398A priority patent/EP1658994A1/fr
Priority to CN200510092314.XA priority patent/CN1769065A/zh
Publication of WO2006046312A1 publication Critical patent/WO2006046312A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to a novel ink jet recording sheet, and more particularly to a high-quality ink jet recording sheet that is excellent in ink absorptivity and bleeding resistance during long-term storage, provides a high image density, and has a small density fluctuation after printing.
  • ink jet recording materials has been rapidly improved and is approaching that of photographic quality.
  • improvements have also been made from the aspect of ink jet recording paper (hereinafter also referred to simply as recording paper), and inorganic fine particles are formed on a highly smooth support.
  • recording paper ink jet recording paper
  • the ink absorbing layer for example, a recording sheet has been devised in which a hydrophilic binder such as gelatin or PVA is applied as an ink absorbing layer on a support having high smoothness to form an ink absorbing layer.
  • a hydrophilic binder such as gelatin or PVA
  • This type of recording paper takes advantage of the swelling properties of the binder.
  • This swelling-type ink absorbing layer has the advantages of high film transparency and high color development because the constituent binder is a water-soluble resin.
  • the ink is difficult to dry after printing, and the formed image and film are weak against moisture, resulting in poor water resistance.
  • a void-type recording paper provided with a porous layer having minute voids as an ink absorbing layer has high ink absorption and high-speed drying properties, but swells due to the refractive index of inorganic fine particles.
  • the film transparency is low, and as a result, the color developability is low.
  • a cationic substance is added to the porous layer and combined with an anionic dye to strongly fix the dye.
  • a method of immobilization is generally used.
  • Typical cationic substances include quaternary ammonium salt polymers, such as “inkjet printer materials and technology” (issued by CMC Co., Ltd. 1 9 9 8 July), or Japanese Patent Laid-Open No. 10-2 1 7 6 0 1 describes the details.
  • a cationic substance is simply added to the porous layer, since the cationic polymer is present in the entire ink absorbing layer, it is difficult to fix the dye at the top, which is satisfactory. At present, the color development is not yet achieved.
  • a method of applying a solution containing a mordant on the ink absorption layer after applying an ink absorption layer coating solution containing silica fine particles and polybutyl alcohol is disclosed (for example, see Patent Document 1). .)
  • the mordant is present in the upper region of the ink absorbing layer, whereby the dye in the landed ink droplet is fixed on the upper portion of the ink absorbing layer, and the resulting print density is adjusted.
  • the purpose is to increase, but such a method is not sufficient to obtain a higher print density. The reason is presumed as follows.
  • boric acid is used as a cross-linking agent for polybulal alcohol, which is a hydrophilic binder, and boric acid is applied simultaneously with the mordant.
  • polybulal alcohol which is a hydrophilic binder
  • boric acid is applied simultaneously with the mordant.
  • polybulal alcohol which is a hydrophilic binder
  • boric acid is applied simultaneously with the mordant.
  • polybral alcohol is crosslinked with boric acid at the time when the mordant and boric acid are applied, the mordant penetrates considerably into the ink absorbing layer, resulting in a print density. I guess that will be insufficient.
  • Patent Document 2 Also disclosed is a method of impregnating more water-soluble organic substances in the vicinity of the surface of the ink absorption layer (see, for example, Patent Document 2).
  • the compound used in the method disclosed in Patent Document 2 is different from the water-soluble polyvalent metal compound according to the present invention, and this organic substance swells at the time of ink absorption, thereby inhibiting the ink absorption rate. The problem is.
  • Patent Document 3 a method in which a water-soluble metal salt such as an aluminum salt is contained in the outermost ink absorbing layer is disclosed (for example, see Patent Document 3).
  • Patent Document 3 does not mention suitability for dye ink, and suggests or mentions the effect of regulating the ratio of water-soluble metal salt to inorganic fine particles within a specific range.
  • Patent Document 4 a method of containing a basic polyaluminum hydroxide compound in the ink absorbing layer
  • Patent Document 5 a method of containing an inorganic mordant and a betaine surfactant in the ink absorbing layer.
  • Each of these methods has a single layer structure as the ink absorbing layer, and the basic polyhydric acid-aluminum compound is a layer containing an inorganic mordant.
  • the method is intended for application by overcoat.
  • Patent Documents 3, 4, and 5 described above describe that the maximum value of the secondary ion intensity derived from the water-soluble polyvalent metal compound of the present invention exists within 10 ⁇ m in the depth direction from the outermost surface.
  • the technical idea is different from the present invention.
  • a method of distributing a large amount of the water-soluble polyvalent metal compound in a region away from the support has been disclosed (for example, refer to Patent Document 6), and the dye in the ink is more fixed on the outermost layer. Is insufficient, and color development is still insufficient.
  • Patent Document 1 Japanese Laid-Open Patent Publication No. 200 1-1632
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2002-144700
  • Patent Document 3 Japanese Patent Laid-Open No. 200 1-28 745 1
  • Patent Document 4 Japanese Patent Publication No. 3-2490 7
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-122520
  • Patent Document 6 Japanese Patent Laid-Open No. 2002-166042
  • the present invention has been made in view of the above problems, and its purpose is excellent in ink absorptivity and bleeding resistance during long-term storage, and a high image density is obtained and density fluctuation after printing is small.
  • the purpose is to provide high-quality ink jet recording paper.
  • ink jet recording paper in which two or more ink absorbing layers containing at least silli force fine particles, a hydrophilic binder and a water-soluble polyvalent metal compound are laminated on a support, the laminated ink absorbing layer group
  • the maximum secondary ion intensity derived from the water-soluble polyvalent metal compound obtained by time-of-flight secondary ion mass spectrometry (TOF—S IMS) in the depth direction is 10 0 from the outermost surface in the depth direction.
  • Ink jet recording paper characterized by being within / m.
  • M represents a divalent or higher-valent metal atom contained in the water-soluble polyvalent metal compound
  • X represents a divalent or higher-valent metal atom M.
  • the ink absorption located at the outermost portion 3.
  • A represents the mass when the water-soluble polyvalent metal compound contained in the ink absorbing layer located at the outermost portion is converted into an oxide
  • B the mass ratio when converted to oxide, the mass ratio [A / (A + B 4)
  • FIG. 1 is a graph showing an example of a secondary ion intensity peak derived from a water-soluble polyvalent metal compound measured by time-of-flight secondary ion mass spectrometry (T OF -S I M S).
  • FIG. 2 is a chart for measuring the distribution of aluminum ion in the depth direction of aluminum ion obtained by TOF_SIMMS measurement of recording paper 2 as a comparative example.
  • FIG. 3 is a chart for measuring the distribution in the depth direction of the ink absorption layer of aluminum ions obtained by TOF-SIMMS measurement of the recording paper 4 of the present invention.
  • TOF-SIMS analysis method
  • the analysis by TOF_SIMS is effective in the present invention, and the present inventors have investigated.
  • the water-soluble polyvalent metal compound is not necessarily localized in the outermost surface area when impregnated with an aqueous solution containing a water-soluble polyvalent metal compound or applied by an overcoat.
  • the film thickness balance between the ink absorbing layer, which is the outermost layer, and other ink absorbing layers is also important for color development and ink absorbing properties.
  • the recording paper of the present invention has a structure in which two or more ink absorption layers containing at least squeezing fine particles, a hydrophilic binder, and a water-soluble polyvalent metal compound are laminated on a support.
  • silica fine particles As silica fine particles according to the present invention, a precipitation method or gel using sodium silicate as a raw material Preference is given to wet silica or gas phase process silica synthesized by the method.
  • a wet silica For example, as a wet silica, Tokuyama Fine Seal manufactured by the sedimentation method is available, and as a silica produced by the gel method, NIPGEL from Nippon Silica Kogyo Co., Ltd. is commercially available.
  • the settling force is approximately 10 to 60 nm, and the gel force is approximately 3 to 1 Onm.
  • There is no particular restriction on the lower limit of the primary particle diameter of wet silica but it is preferably 3 nm or more from the viewpoint of production stability of silica particles, and preferably 50 nm or less from the viewpoint of film transparency.
  • wet silica synthesized by the gel method tends to have a smaller primary particle size as compared to the sedimentation method.
  • Vapor phase silica is synthesized by combustion using silicon tetrachloride and hydrogen as raw materials.
  • Aerosil series manufactured by Nippon Aerosil Co., Ltd. is commercially available.
  • gas phase method silica is particularly preferable from the viewpoint that a high porosity is obtained and that coarse aggregates are not easily formed when a cationic composite fine particle dispersion is produced.
  • Vapor phase silica is characterized by its ability to disperse with low energy with respect to wet silica because secondary agglomerates are relatively weak against wet silica forces! ing.
  • Vapor phase fine particles are preferably those with an average primary particle size of 3 to 50 nm. If the average particle size of the primary particles is 50 nm or less, high glossiness of the recording paper can be achieved, and reduction in the maximum density due to irregular reflection on the surface can be reduced. Images can be obtained.
  • the average particle size of the squeezing force fine particles is determined by observing the cross section or the surface of the particle itself or the formed ink absorption layer with an electron microscope, and measuring the particle size of arbitrary tens of siri force particles. Is obtained as its simple average (number average).
  • each particle size is expressed as a diameter assuming a circle equal to the projected area.
  • the average particle size is 20 to 200 nm. This is preferable from the viewpoint of obtaining a recording sheet that achieves gloss.
  • the amount of silica fine particles added depends on the required ink absorption capacity, porosity of the void layer, and the type of hydrophilic binder. Generally, 5 to 30 g per lm 2 of recording paper, preferably 10 to 2 5 g.
  • the ratio between the silica fine particles and the hydrophilic binder used in the ink absorbing layer is approximately 2: 1 to 20: 1 in terms of mass ratio, and particularly preferably 3: 1 to 10: 1.
  • a preferable porosity is 40 to 75%.
  • the porosity can be appropriately adjusted to a desired condition depending on the type of silica fine particles to be selected, the type of hydrophilic binder, the mixing ratio thereof, or the amount of other additives.
  • the porosity referred to in the present invention is the ratio of the total volume of voids to the volume of the void layer, and is calculated from the total volume of the constituents of the layer and the thickness of the layer. The total volume of the voids can be easily obtained by measuring the amount of water absorption.
  • hydrophilic binder used in the ink jet recording paper of the present invention will be described.
  • hydrophilic binder of the present invention examples include polybulal alcohol, gelatin, Polyethylene oxide, Polybulol pyrrolidone, Casein, Starch, Agar, Carrageenanane, Polyacrylic acid, Polymethallylic acid, Polyacrylamide, Polymethacrylate glycol, Polystyrene sulfonic acid, Cellulose, Hydroxyethyl senolose, Examples include force noreboxino retinoyl cellulose, hydroxy / reety / rese / relose, dextran, dextrin, pullulan, and water-soluble polyvinyl butyral. Two or more of these hydrophilic binders can be used in combination.
  • the hydrophilic binder that is preferably used in the present invention is polyvinyl alcohol, and in addition to the usual polybulal alcohol obtained by hydrolyzing polyvinyl acetate, the anion having a cation-modified polyvinyl alcohol anionic group. Also included are modified polyvinyl alcohols such as modified polyvinyl alcohol and UV-crosslinked modified polybutyl alcohol.
  • Polyvinyl alcohol obtained by hydrolysis of vinyl acetate is preferably one having an average degree of polymerization of 100 ° or more, and particularly preferably having an average degree of polymerization of 15500 to 500, Further, those having a saponification degree of 70 to 100% are preferred, and those having a saponification degree of 80 to 99.5% are particularly preferred.
  • Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups described in JP-A-61-104083.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl (2-acrylamido 2,2-dimethylethyl) ammonium chloride, trimethyl mono (3-acrylamido 3,3-dimethylpropyl).
  • Ammonium chlora Id N-vinylimidazole, N-bi-l-2-methylimidazole, N- (3 dimethylaminopropyl) metathalamide, hydroxyethyl trimethyl ammonium chloride, trimethyl (2-methacrylamidopropyl) ) Ammonium chloride, N— (1,1_dimethyl-3-dimethylaminopropyl) atrylamide, and the like.
  • the ratio of cation-modified group containing monomers of cation-modified polyvinyl alcohol is 0 for vinyl acetate. 1-1 0 mole 0/0, preferably from 0.2 to 5 mol 0/0.
  • anion-modified polybulal alcohol examples include polybulal alcohol having an anionic group as described in JP-A No. 1-20600 8 and JP-A No. 6-2 3 7 6 8 1. And copolymers of butyl alcohol and a vinyl compound having a water-soluble group, as described in JP-A-7-3 8 7 9 79, and JP-A-7-2 8 5 2 6 5 And modified polybulal alcohol having a water-soluble group.
  • Nonionic modified polybulal alcohols include, for example, polybulur alcohol derivatives in which a polyalkylene oxide group is attached to a part of vinyl alcohol as described in JP-A-7-9758, Examples thereof include a block copolymer of a butyl compound having a hydrophobic group and vinyl alcohol described in JP-A-8-257597.
  • UV-crosslinking modified polybulal alcohol examples include a modified polybulal alcohol having a photoreactive 'f raw side chain as described in Japanese Patent Application Laid-Open No. 2000-0 2 6 2 2 3 6. It is done.
  • polyvinyl alcohol may be used in combination of two or more types having different types of polymerization and modification as described above.
  • the ink jet recording paper of the present invention is excellent in glossiness, and in order to achieve a high porosity without deteriorating the brittleness of the film, it is preferable that polybulal alcohol is hardened with a hardener.
  • the hardener that can be used in the present invention is generally a compound having a group capable of reacting with polyvinyl alcohol, or a compound that promotes the reaction between different groups of polyvinyl alcohol.
  • Epoxy hardeners eg diglycidino retinoyl ether, ethylene glyconoresiglycidyl etherol, 1,4-pentanediol diglycidyl ether, 1,6-diglycidyl hexane, N, N —Diglycidyl 4-glycidyloxydiline, sorbitol polyglycidyl ether, glyceryl polyglycidyl ether, etc.), aldehyde hardeners (eg formaldehyde, darioxal, etc.), active halogen hardeners (eg 2,4-dichloro-4-hydroxy-1,3,5-s-triazine, etc.
  • Active vinyl compounds for example, 1,3,5-trisatariloy hexahexahydro-s-triazine, bisvinylsulfur methyl ether, etc.
  • boric acid and its salts for example, borax, aluminum alum, isocyanate Compounds and the like.
  • boric acid and its salts, epoxy hardeners and isocyanate compounds are preferred.
  • boric acid and its salts include oxyacids and their salts with a boron atom as the central atom, specifically orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, octaboric acid and their salts. Contains salt.
  • the amount of hardener used varies depending on the type of polyvinyl alcohol, type of hardener, type of silica fine particles, ratio to polyvinyl alcohol, etc. Usually 5 to 50 O mg per gram of polyvinyl alcohol, preferably Is 10-30 O mg.
  • a water-soluble coating solution containing no hardener for forming an ink absorbing layer is applied and dried, and then a solution containing a hardener is overcoated. Can be supplied.
  • the ink jet recording paper of the present invention is characterized by containing a water-soluble polyvalent metal compound.
  • water-soluble polyvalent metal compound examples include aluminum, calcium, magnesium, zinc, iron, strontium, barium, nickel, copper, scandium, gallium, indium, titanium, zirconium, tin, lead, and other hydrochloric acid. Salts, sulfates, nitrates, acetates, formates, succinates, malonates, and acetates. Of these, water-soluble salts composed of aluminum, calcium, magnesium, zinc, and zirconium are preferred because their metal ions are colorless. Furthermore, a water-soluble aluminum compound and a water-soluble zirconium compound are particularly preferable in that they have excellent bleeding resistance during long-term storage.
  • water-soluble aluminum compounds include polyaluminum chloride (basic aluminum chloride), aluminum sulfate, basic aluminum sulfate, potassium aluminum sulfate (miyoban), ammonium aluminum sulfate (ammonium aluminum pan), sulfuric acid Examples thereof include sodium aluminum, aluminum nitrate, aluminum phosphate, aluminum carbonate, polysulfuric acid aluminum silicate, aluminum acetate, and basic aluminum lactate.
  • the water solubility in the water-soluble polyvalent metal compound means that it dissolves in 20 ° C. water at 1% by mass or more, more preferably 3% by mass or more.
  • the most preferable water-soluble aluminum compound is basic aluminum chloride having a basicity of 80% or more from the viewpoint of ink absorption, and can be represented by the following molecular formula. [A 1 2 (OH) n C 16— n] m
  • the water-soluble zirconium compound are preferably zirconyl carbonate, zirconyl carbonate ammonium, zirconyl acetate, zirconyl nitrate, zirconium chloride, zirconyl lactate and zirconate citrate. Particularly preferred are zirconium carbonate and zirconium acetate. In particular, acid zirconium salt and zirconyl acetate are preferred from the viewpoint of bleeding resistance during long-term storage.
  • the distribution state of the water-soluble polyvalent metal compound in the ink absorbing layer group composed of two or more layers is determined under a specific condition, that is, the flight in the depth direction of the laminated ink absorbing layer group.
  • the maximum secondary ion intensity derived from the water-soluble polyvalent metal compound obtained by time-type secondary ion mass spectrometry (TO F 1 SI MS) is within 10 ⁇ in the depth direction from the outermost surface.
  • the water-soluble polyvalent metal compound contained in the ink absorbing layer located at the outermost part is a mass in the oxide conversion of the polyvalent metal compound.
  • 0.1 to 1.0 gZm 2 is preferable. 0. 1 g / m 2 in terms of the image density in the following, also 1. O gZm difference in performance occurs in terms of 2 or more in the ink absorbent.
  • a water-soluble polyvalent metal can be contained in the ink absorbing layer other than the outermost polishing within the range satisfying the conditions specified in the present invention.
  • the mass when the water-soluble polyvalent metal compound contained in the ink absorbing layer located at the outermost portion is converted to oxide is A, and the outermost portion
  • the mass ratio of the total water-soluble polyvalent metal compound contained in all of the ink absorbing layers except for the ink absorbing layer located at is [A / (A + B)] is preferably 0.5 or more, more preferably ⁇ 60. In any of the above cases, it is necessary to have a clear ion intensity peak within 10 ⁇ from the outermost surface.
  • FIG. 1 is a graph showing an example of a profile of secondary ion intensity derived from a water-soluble polyvalent metal compound measured by time-of-flight secondary ion mass spectrometry (TOF—SIMS).
  • the horizontal axis represents the measurement distance (/ m) from the outermost surface to the depth direction
  • the vertical axis represents the time-of-flight secondary ion mass spectrometry (TOF_SIMS) at each depth position.
  • TOF_SIMS time-of-flight secondary ion mass spectrometry
  • the profile B of the ink absorbing layer according to the present invention which is composed of two or more ink absorbing layers and is practiced by adding a high concentration polyvalent metal compound to the outermost layer, Since the maximum secondary ion intensity derived from the polyvalent metal compound exists within a depth of 1 ⁇ ⁇ from the outermost surface (in Fig. 1, at a depth of about 6 ⁇ ⁇ ), The ink that landed on the surface was fixed in the surface area of the ink absorbing layer, and as a result, a high image density could be obtained.
  • the ratio force between the water-soluble polyvalent metal compound and the silica fine particles contained in the ink absorbing layer located on the outermost part of the two or more laminated ink absorbing layers is preferable that the mass ratio when converted into the respective acid compounds satisfies the condition defined by the following formula (1).
  • M represents a divalent or higher metal atom contained in the water-soluble polyvalent metal compound
  • X represents a divalent or higher metal atom M.
  • the oxide of the water-soluble polyvalent metal compound here is represented by M0x / 2 in the above formula (1), and examples of the divalent metal oxide include CaO, MgO, and ZnO. Examples of the trivalent metal oxide include A 1 2 0 3 .
  • Z R_ ⁇ 2 As the tetravalent metal oxides, for example, Z R_ ⁇ 2.
  • MO x / 2 according to equation (1) the number of oxygen atoms is displayed as a fraction for metal atoms having an odd valence, but in this case, it is displayed as an integer according to convention.
  • acid aluminum is AI OL 5 according to the display method of formula (1), but in this case, it is displayed as A 1 2 0 3 .
  • the water-soluble polyvalent metal compound content in the depth direction of the ink absorbing layer specified in the present invention is measured using an electron probe microanalyzer (EPMA) or flight time for a sample obtained by trimming the side of an ink jet recording paper with a microtome or the like. It can be measured by determining the distribution of elements specific to polyvalent metals or specific secondary ion fragments in the thickness direction of the ink absorption layer using a scanning secondary ion mass spectrometer (TO F-S IMS) .
  • EPMA electron probe microanalyzer
  • TO F-S IMS scanning secondary ion mass spectrometer
  • TOF S IM S preferred ionic species as primary ions during measurement A u +, I nT, C s +, is a metal ionic species, such as G a +, these I n +, Ga + are preferred.
  • the preferred secondary ion to be detected is selected from the secondary ion mass spectrum of the polyvalent metal measured in advance.
  • the acceleration voltage of primary ions is preferably 20 kV to 30 kV, and various adjustments are preferably performed so that the beam diameter measured by the knife edge method is 0.25 m or less.
  • Irradiation conditions such as beam current and irradiation time are arbitrary. As a typical example, a primary ion beam current of 0.9 nA, an irradiation time of 20 minutes and the like are preferable measurement conditions.
  • the ink jet recording paper or the ink absorbing layer is poor in electrical conductivity, so that it is preferable to appropriately perform charge neutralization such as using a neutralizing electron gun.
  • the primary ion beam is scanned within a range where the entire ink absorption layer can be measured. Typically, a 40 / m square area is scanned. It is possible to obtain an image of chemical species present in the ink absorbing layer from the scanning position of the primary ion beam and the detected secondary ions. An image of a chemical species is obtained by obtaining a secondary ion mass spectrum at 256 X 256 points in the scanning region and recording the intensity of the desired secondary ion peak from the mass spectrum. . Furthermore, by integrating the peak intensity at the same thickness from this image, a profile in the thickness direction of a specific secondary ion can be obtained. Secondary ion image creation and profile creation are usually secondary ions This is a function attached to software for data processing of the mass spectrometer, and this function can also be used in the present invention.
  • the position of the ink absorption layer and the thickness of the ink absorption layer are the regions where metal ions contained in the silica fine particles present in the ink absorption layer are detected, as in the case of the polyvalent metal.
  • the position of each layer is 50% of the integrated ion intensity in the profile in the thickness direction.
  • the dry film thickness of the outermost layer according to the present invention is preferably 2 to 20%, more preferably 5 to 15% of the total dry film thickness of all the ink absorbing layers. That is, by laminating two or more ink absorbing layers and containing the water-soluble polyvalent metal compound in a high concentration in the outermost layer of the ink absorbing layer, the surface of the ink absorbing layer as shown in FIG. An ink absorbing layer in which the maximum value of the secondary ion intensity derived from the polyvalent metal compound appears in the region can be realized.
  • the outermost layer of the ink absorbing layer according to the present invention preferably contains a surfactant.
  • a surfactant that can be used in the ink absorbing layer, any of cationic, betaine, and nonionic hydrocarbon, fluorine, and silicon surfactants can be used. Of these, cationic and betaine surfactants described in JP-A-2003-312134 are preferred from the viewpoints of coating film quality such as coating failure resistance and suitability for simultaneous multilayer coating.
  • the amount of surfactant 0. 0001 ⁇ 1. 0 g "m 2 are preferred, More preferably 0. 001 ⁇ 0. 5 gZm 2.
  • the structure of the ink absorbing layer according to the present invention include, for example, a method described in JP-A No. 11-321079, JP-A No. 2000-158807, and the like.
  • a porous ink absorbing layer containing a polymer can be used.
  • the cationic polymer is a polymer having a primary to tertiary amine, a quaternary ammonium base, or a quaternary phosphonium base in the polymer main chain or side chain, and a known compound is used in ink jet recording paper. It is done. From the standpoint of ease of manufacture, those that are substantially water-soluble are preferred.
  • cationic polymers examples include polyethyleneimine, polyallylamine, polyvieramine, dicyandiamide polyalkylene polyamine condensate, polyalkylene polyamine dicyandiammonium salt condensate, dicyandiaformaline condensate, epichlorohydrindialkylamamine.
  • Diaryldimethylammonium chloride polymer Diaryldimethylammonium chloride ⁇ SO 2 copolymer
  • Polyvinylimidazole Vinylpyrrolidone-Vinylimidazole copolymer
  • Polyburepyridine Polyamidine, Chitosan, Cationization Starch
  • berylbenzyltrimethylammonium chloride polymer (2-metachlorooxyethyl) trimethylammonium chloride polymer, dimethylamino Chirumetaku Relate polymer, and the like.
  • the average molecular weight of the cationic polymer should be in the range of 2000 to 500,000 Is more preferable, and the range of 10,000 to 100,000 is more preferable.
  • the average molecular weight referred to in the present invention is the number average molecular weight, and refers to a polyethylene glycol conversion value obtained from gel permeation chromatography.
  • the cationic polymer When the cationic polymer is added to the coating solution in advance, it may be added not only uniformly to the coating solution but also in the form of forming composite particles with inorganic fine particles.
  • a method for preparing composite particles using inorganic fine particles and force thionic polymer a method of mixing inorganic fine particles with a cationic polymer and adsorbing and coating, and a method of aggregating the coated particles to obtain higher order composite particles
  • cationic polymers generally have water-soluble groups, they have water-solubility, for example, they may not dissolve in water depending on the composition of the copolymerization component. Although it is preferable that it is water-soluble from the viewpoint of ease of production, even if it is hardly soluble in water, it can be dissolved in a water-miscible organic solvent and used.
  • the water-miscible organic solvent here means alcohols such as methanol, ethanol, isopropanol and n-propanol, glycols such as ethylene glycol, diethylene glycol and glycerin, esters such as ethyl acetate and propyl acetate, acetone,
  • An organic solvent that can dissolve approximately 10% or more in water such as ketones such as methyl ethyl ketone and amides such as N, N-dimethylformamide.
  • the amount of organic solvent used is preferably less than the amount of water used.
  • the cationic polymer is usually used in the range of 0.1 to 1 O g, preferably 0.2 to 5 g, per lm 2 of the ink jet recording paper.
  • an image storability improving agent such as an ultraviolet absorber, an antioxidant, and a anti-smudge agent.
  • UV absorbers, antioxidants, and anti-smudge agents include alkylated phenol compounds (including hindered phenol compounds), alkylthiomethyl phenol compounds, hydroquinone compounds, alkylated hydroquinone compounds, and tocophorol compounds.
  • alkylated phenol compounds compounds having two or more thioether bonds, bisphenol compounds, ascorbic acid, amine-based antioxidants, water-soluble or hydrophobic metal salts, organometallic compounds, metal complexes , Hindered amine compounds, hydroxyamine compounds, polyamine compounds, thiourea compounds, urea compounds, hydra
  • a zido compound a hydroxybenzoic acid compound, a dihydroxybenzoic acid compound, a trihydroxy benzoic acid compound, and the like.
  • polystyrene polyacrylic acid esters, polymethacrylic acid esters, polyacrylamides, polyethylene, polypropylene, polysalt-vinyl, polysalt-vinylidene, or a copolymer thereof, urea resin, melamine resin, etc.
  • JP-A-4-219266 such as optical brightener, sulfuric acid, phosphoric acid, citrate, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.
  • Various known additives such as a pH adjuster, an antifoaming agent, a P-preservative, a thickener, an antistatic agent, and a matting agent can also be contained.
  • the support used for the recording paper of the present invention will be described.
  • the support that can be used in the present invention.
  • a water-absorbing support such as paper
  • the method using a non-water-absorbing support as the support is preferable in that the effect of the present invention is remarkably exhibited.
  • a conventionally known ink recording sheet can be appropriately used.
  • Examples of the water-absorbing support that can be used in the present invention include a force that can include, for example, a sheet of paper, cloth, wood, and the like. It is most preferable because it is excellent.
  • the main raw materials for paper support are chemical pulps such as LBKP and NBKP, mechanical pulps such as GP, CGP, RMP, TMP, CTMP, CMP, and PGW, and wood pulp such as waste paper pulp such as DIP. Things can be used.
  • various fibrous materials such as synthetic pulp, synthetic fiber, and inorganic fiber can be appropriately used as a raw material as required.
  • additives such as sizing agents, pigments, paper strength enhancers, fixing agents, fluorescent whitening agents, wet paper strength agents, and cationizing agents are added to the paper support as necessary. can do.
  • the paper support can be produced by mixing various fibrous materials such as wood pulp and various additives and using various paper machines such as a long net paper machine, a circular net paper machine, and a twin wire paper machine. If necessary, it can be subjected to size press treatment with starch, polybulu alcohol, etc., various coating treatments, or calendar treatment on the paper making stage or paper machine.
  • non-water-absorbing support examples include a plastic resin film support or a support in which both sides of paper are covered with a plastic resin film.
  • plastic resin film support examples include a polyester film, a polyvinyl chloride film, a polypropylene film, a cellulose triacetate film, a polystyrene film, and a film support in which these are laminated. This These plastic resin films can be transparent or translucent.
  • a particularly preferred support in the present invention is a support in which both sides of paper are coated with a plastic resin, and most preferred is a support in which both sides of paper are coated with a polyolefin resin.
  • a non-water-absorbing paper support laminated with polyethylene which is the most preferred polyolefin resin, will be described.
  • the base paper used for the paper support is made from wood pulp as the main raw material, and if necessary, synthetic pulp such as polypropylene or synthetic fibers such as nylon or polyester is added to the wood pulp.
  • synthetic pulp such as polypropylene or synthetic fibers such as nylon or polyester is added to the wood pulp.
  • wood pulp for example, any of LBKP, LBS P, NBKP, NB SP, LDP, NDP, LUKP, N'UKP can be used, but LBKP, NB SP, LBSP, NDP, LDP with a lot of short fibers. It is preferable to use more.
  • the ratio of LBSP or LDP is preferably 10% by mass or more and 70% by mass or less.
  • the pulp is preferably a chemical pulp (sulfate pulp or sulfite pulp) with few impurities, and a pulp having a whiteness improved by bleaching is also useful.
  • sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, tanolec, and titanium oxide, paper strength enhancers such as starch, polyacrylamide, and polyvinyl alcohol, fluorescent whitening agents, polyethylene Water retaining agents such as glycols, dispersants, softening agents such as quaternary ammonia can be added as appropriate.
  • the freeness of pulp used for papermaking is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is 24% residual mass by mass defined in JIS-P-8207.
  • the sum of the 42% mesh residue and 30% to 70% by mass is preferred.
  • the mass% of the 4 mesh residue is preferably 20% by mass or less.
  • the basis weight of the base paper is preferably 50 to 250 g, particularly preferably 70 to 200 g.
  • Base paper The thickness is preferably 50 to 210 ⁇ .
  • the base paper can be calendered at the paper making stage or after paper making to give a high smoothness.
  • the density of the base paper is 0.7 to 1.2 g / cm 3 (according to the method specified in JI SP-81 18).
  • the stiffness of the base paper is preferably 20 to 200 g under the conditions specified in JIS-P-8143.
  • a surface size agent may be applied to the base paper surface.
  • the surface sizing agent the same sizing agent that can be added to the above-mentioned base paper can be used.
  • the pH of the base paper is measured by the hot water extraction method specified in JI SP-81 13. In this case, it is preferably 5 to 9.
  • the polyethylene covering the front and back of the base paper is mainly low-density polyethylene (LDPE) or high-density polyethylene (HDPE), but some other LLDPE and polypropylene can also be used.
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • the polyethylene layer on the side where the ink absorbing layer is applied is improved in opacity and whiteness by adding rutile or anatase type titanium oxide into polyethylene, as is widely done in photographic paper. Is preferred. Amount containing titanium oxide, 1 to 20 mass relative to poly ethylene 0/0, preferably from 2 to 5 wt%.
  • high heat resistance, facial and fluorescent whitening agent for adjusting the white background can be added.
  • coloring pigments include ultramarine blue, bitumen, cobalt blue, phthalocyanine pnnore, manganese bunoley, cenorelian, tungsten punolei, molyb dimple, and anthraquinone blue.
  • Optical brighteners include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-1-alkoxy-1,1,8-naphthalenedicarboxylic acid 1-N-alkyl imide, bisbenzoxazolylethylene, dialkyl And stilbene.
  • the amount of polyethylene used on the front and back of the paper is determined after the thickness of the ink absorption layer and the pack layer are provided.
  • the thickness of the polyethylene layer is 1 55 50 on the ink-absorbing layer side; um, 10 0 40 ⁇ on the pack layer side
  • the ratio of the front and back polyethylene is preferably set so as to adjust the curl that changes depending on the type and thickness of the ink absorbing layer, the thickness of the inner paper, etc. Is approximately 3/1 1/3 in thickness.
  • the polyethylene-coated paper support preferably has the following characteristics.
  • Tensile strength J I S — ⁇ — 8 1 1 3 strength, preferably 20 3 0 ON in the vertical direction and 1 0 20 ON in the horizontal direction
  • Tear strength as defined by JIS—P—8 1 1 6, preferably 0.1 2 N in the vertical direction and 0.2 2 N in the horizontal direction
  • the transmittance for light in the visible range is 20% or less, especially 15% or less.
  • the binder for the undercoat layer is preferably a hydrophilic polymer such as gelatin or polybutyl alcohol, or a latex polymer having a Tg of 30 to 60 ° C. These binders are used in the range of 0.001 to 2 g per lm 2 of the recording medium.
  • the undercoat layer can contain a small amount of a conventional antistatic agent such as a cationic polymer for the purpose of antistatic.
  • a pack layer may be provided on the surface of the support opposite to the side of the ink absorbing layer for the purpose of improving the slipperiness and charging characteristics.
  • gelatin is a hydrophilic polymer such as polybulal alcohol, and Tg is 30-60.
  • C latus polymer is preferable, and an antistatic agent such as a cationic polymer, various surfactants, and a matting agent having an average particle size of about 0.5 to 20 ⁇ m can be added.
  • the thickness of the back layer is generally 0.1 to 1 im, but when the back layer is provided to prevent curling, it is generally in the range of 1 to 20 Aim.
  • the back layer may be composed of two or more layers.
  • each constituent layer including an ink absorbing layer can be produced by individually or simultaneously selecting from a known coating method and coating and drying on a support.
  • coating methods include roll coating method, rod bar coating method, air knife coating method, spray coating method, curtain coating method, or US Pat. Nos. 2,761,419 and 2,761,791
  • the slide bead coating method using the hopper described in 1), the extrusion coating method, etc. are preferably used.
  • the viscosity of each coating solution when two or more constituent layers are applied simultaneously is preferably in the range of 5 to 100 mPa ⁇ s, more preferably 10 to 5 OmP a ⁇ s range. Also, using the curtain coating method In this case, the range of 5 to 1200 mPa * s is preferable, and the range of 25 to 50 OmPa * s is more preferable.
  • the viscosity at 15 ° C of the coating solution is preferably 10 OmPa ⁇ s or more, more preferably 100 to 3,00 OmPa ⁇ s, and still more preferably 3,000 to 3,000 Ompa ⁇ s. And most preferred is 10,000 to 30,000 m Pa's.
  • the coating liquid is heated to 30 ° C or higher, and after simultaneous multi-layer coating, the temperature of the formed coating film is once cooled to 1 to 15 ° C, and then 10 ° C or higher. It is preferable to dry with. Preparation, coating, and drying of the coating solution at a temperature below the Tg of the thermoplastic resin so that the thermoplastic resin contained in the surface layer does not form a film during preparation of the coating solution, during coating, and during drying. It is preferable. More preferably, the drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. Further, as a cooling method immediately after coating, it is preferable to carry out a horizontal setting method from the viewpoint of the uniformity of the formed coating film.
  • the heating condition is not particularly limited as long as it is stored at a temperature of 35 ° C or higher and 70 ° C or lower for 24 hours or longer and 60 days or shorter, but a preferable example is, for example, 36 ° C for 3 days. ⁇
  • Example 4 4 weeks at 40 ° C for 2 days to 2 weeks, or 55 ° C for 1 to 7 days.
  • the curing reaction of the water-soluble binder can be accelerated or the crystallization of the water-soluble binder can be promoted, and as a result, a preferable ink absorbability can be achieved.
  • a silica dispersion D-2 was prepared in the same manner as in the preparation of the silica dispersion D-1, except that the light-on fluorescent brightener was omitted.
  • silica dispersions D_l, D_2, and D-3 prepared above the dispersion state of the silica particles was observed according to the method described in JP-A-11-32 1079. As a result, extremely stable force thione converted composite particles I was able to confirm that The silica dispersions D-1, D-2 and D-3 prepared above were filtered using a TCP-30 type filter manufactured by Advantech Toyo Co., Ltd. having a filtration accuracy of 30 ⁇ .
  • each addition amount was displayed as the amount per 1 L of coating solution.
  • Silica Dispersion D 1 650 ml polyvinyl alcohol (average polymerization degree: 3800 saponification degree 88%) 8.0% aqueous solution 250 ml Surfactant (manufactured by Neos; Phtergent 400 S) 4% aqueous solution 2. Finished to 1000ml with 0ml pure water
  • Silica Dispersion D 2 630 ml Polyvinyl alcohol (average polymerization degree: 3800 Saponification degree 88%) 8.0% aqueous solution-250 ml Surfactant (Kao; Cotamin 24P) 6% aqueous solution 3. Oml Surfactant 4% aqueous solution of (Neos; Aftergent 400 S)
  • Each of the ink absorbing layer coating solutions prepared as described above has a filtration accuracy of 20 ⁇ .
  • the mixture was filtered through a TC PD-30 filter manufactured by Dobantech Toyo, and then filtered through a TC PD-10 filter.
  • each of the prepared ink absorbing layer coating liquids was placed on a paper support (RC paper) coated with polyethylene on both sides at 40 ° C. so that the wet film thickness described below was obtained.
  • a coater Using a coater, four layers were applied simultaneously.
  • Second layer 4 2 ⁇ ⁇ (S i 0 2 Amount: 4.57 g / m 2 )
  • 3rd layer 40 ⁇ . ⁇ (S i 0 2 weight: 4.40 g / m 2 )
  • the RC paper used was the following support wound on a roll having a width of about 1.5 m and a length of about 400 Om.
  • the RC paper used had a moisture content of 8% and a basis weight of 1700 g of photographic paper. Extruded and melted polyethylene containing 6% anatase-type titanium oxide at a thickness of 35 m. ⁇ Coated On the back surface, polyethylene having a thickness of 40 zm was extruded and melt coated at a thickness of 35 ⁇ .
  • Drying after applying the coating solution for the ink absorbing layer is performed by passing through a cooling zone maintained at 5 ° C for 15 seconds to reduce the film surface temperature to 13 ° C, and then using multiple drying zones. temperature was appropriately set and dried, and then rolled up to obtain a recording paper 1.
  • the total dry thickness of the ink absorption layer thus formed was 42.5 ⁇ , and the dry thickness of the fourth layer (outermost layer) was 11.5 ⁇ m.
  • the recording paper 1 does not contain any water-soluble polyvalent metal compound in all layers.
  • a basic aluminum chloride aqueous solution (manufactured by Taki Kagaku: Takipine # 1 5 0 0, ⁇ 1 2 ⁇ 3 contains 2 3.7 5%, basicity 8 3 . 5%) was overcoated to be 0. 5 g / m 2 in a 1 2 0 3 amount with terms, to produce a record sheet 2.
  • Recording paper 3 was prepared in the same manner as recording paper 1 except that the silica dispersion D-2 in the fourth layer was changed to silica dispersion D-3.
  • Recording paper 4 was produced in the same manner except that the content was changed to 4%). Incidentally, 2. 4 0 gZm 2 minutes of the silica fine particles is equally distributed to the first to third layers, and the same total S i 0 weight with 2. A (A + B) of recording paper 4 is 1.0.
  • Recording paper 5 was prepared in the same manner as recording paper 1, except that the third-layer silica dispersion D-2 was changed to silica dispersion D_3.
  • 2. 40 g / m 2 min of the silica microparticles is the first layer, second layer, and equally distributed to the fourth layer, and the same total S I_ ⁇ weight with 2.
  • AZ (A + B) of recording paper 6 is 0.
  • the basic salt / hyalum aqueous solution (made by Taki Chemical: Takibine # 1500, A1 2 0 3 containing 23.75%, basicity 83 ., the same procedure of 5%) was added which had to be 0. OS gZm 2 in a 1 2 0 3 amount with terms, to produce a recording paper 7.
  • the AZ (A + B) of the recording paper 7 is 0.9.
  • the basic layer-aluminium aqueous solution made by Taki Chemical: Takibine # 1500, A1 2 0 3 containing 23.7% 5% in the third layer ink absorbing layer coating solution, base
  • the recording paper 8 was prepared in the same manner except that the amount was adjusted to 0.75 gZm 2 in terms of Al 2 0 3 conversion.
  • the basic layer-aluminum aqueous solution (made by Taki Chemical: Takibine # 1500, Takibine # 1500, 23.75% contained as% 1 2 ⁇ 3 , 82.5%) is added to 0.5 g / m 2 in terms of A 1 2 0 3 conversion amount, the amount of Si 0 2 is 2.0 g / m 2 , and the dry film thickness is 4
  • Recording paper 9 was produced in the same manner except for O / zm. Incidentally, 2. 4.0 g / m 2 min of the silica fine particles is equally distributed to the first to third layers, and the same total S I_ ⁇ weight with 2.
  • the AZ (A + B) of recording paper 9 is 1.0.
  • the cross-section of the ink absorption layer is TRI FT-II manufactured by Pysica 1 E 1 ectronics.
  • Ion species In The distribution of the aluminum ion ink absorption layer in the depth direction was determined by TOF-SIMS measurement under the condition of acceleration voltage: 25 kV. As a result, it was confirmed that the recording paper of the present invention had a maximum value of secondary ion intensity derived from aluminum ions within 10 / zm in the depth direction from the outermost surface.
  • FIGS. 2 and 3 show distribution measurement charts of the polyvalent metal compound of the comparative recording sheet 2 and the recording sheet 4 of the present invention.
  • Fig. 2 shows the distribution measurement chart in the depth direction of the ink absorption layer of aluminum ions obtained by TOF-S IMS measurement of recording paper 2 as a comparative example.
  • the outermost layer is the right edge of the chart, and the length of the support surface is represented by Lengh O C ⁇ m).
  • Lengh O C ⁇ m the length of the support surface
  • Fig. 3 shows the aluminum obtained by TO F-S IMS measurement of recording paper 4 of the present invention.
  • 2 shows a distribution measurement chart in the depth direction of a muon ink absorbing layer.
  • the outermost layer is the right end of the chart, and Length O (, am) represents the support surface.
  • the secondary ion signal derived from aluminum ion is very much expressed in the region from the outermost surface to a depth of 10 m, and the basic aluminum chloride is distributed in the surface region.
  • the line width with a solid image of a single pull with pure ink is approximately 0.3 mm.
  • the black line was printed, air dried for 1 hour, and inserted into a transparent clear file. Leave this as a clear file in an environment of 40 ° C and 80% RH for 1 week, and measure the black line width with a microphone mouth densitometer before and after storage (the reflection density is 50% of the maximum density).
  • the width of this part was taken as the line width), and the rate of change of the line width expressed by the following equation was calculated, and this value was used as a measure for the resistance to bleeding after long-term storage. The smaller this value is, the better the bleeding resistance is, and the level of no problem in practical use is 130 or less.
  • Line width change rate 2 (Line width of the black line after saving / Line width of the black line before saving) X 100
  • Yellow, magenta, and cyan solid images were printed with genuine ink using Seiko Epson's ink jet printer PM-950C, and after printing, 0.5 hours in an environment of 23 ° C and 55% RH. Left for 24 hours.
  • the density of each yellow, magenta, and cyan was measured with a reflection densitometer for each color density D (0.5) after 0.5 hours and each color density D (24) after 24 hours.
  • D (24) / D (0.5) X I 00 was determined for each color image, and was used as the density reduction rate.
  • the average density reduction rate D (a v e) for yellow, magenta, and cyan was determined and used as a measure of density stability after printing. The closer D (Ave) is to 100, the smaller the density fluctuation after printing and the better the density stability.
  • Table 1 shows the evaluation results excluding the measurement of polyvalent metal compound distribution in the ink absorption layer obtained as described above. ⁇ table 1 ⁇
  • Example 1 a basic aluminum chloride aqueous solution that is a water-soluble polyvalent metal compound (manufactured by Taki Chemical Co., Ltd .: 2. 3.75% as tachypine # 1 500 A 1 2 0 3 , basicity 83. 5%), instead of basic aluminum lactate (manufactured by Taki Kagaku: Taxelum G-17 L; basicity 72%), zircolacetate (Daiichi Rare Element Chemical Co., Ltd .: Zircozol ZA), Zirconate oxychloride (Daiichi Rare Element Chemical Industry: Zircosol ZC-2), Recording paper 13 16 was prepared and evaluated in the same manner as in the method described in Example 1.
  • Recording papers 1 3 to 15 Recording papers 1 3 to 15 were all as good as recording paper 4 listed in Table 1.
  • Recording paper 16 using magnesium chloride as a water-soluble polyvalent metal has the same level of color development and bleeding resistance as recording paper 3, but the ink absorbency and density stability are similar to those of recording paper 4. Obtained. Industrial applicability
  • the present invention it is possible to provide a high-quality ink jet recording sheet that is excellent in ink absorbability and bleeding resistance during long-term storage, provides a high image density, and has a small density fluctuation after printing.

Abstract

La présente invention concerne un papier pour impression à jet d’encre comprenant un support et, superposées sur celui-ci, deux couches d’absorption ou plus, chacune comprenant au moins des microparticules de silice, un liant hydrophile et un composé métallique polyvalent soluble dans l'eau, caractérisé en ce que dans le sens de profondeur du groupe de couches stratifiées d'absorption de l’encre, la valeur maximale de la force de l’ion secondaire, telle que déterminée par spectrométrie de masse ionique secondaire à temps de vol (TOF-SIMS), dérivée à partir du composé métallique polyvalent soluble dans l'eau, repose à moins de 10 µm dans le sens de la profondeur de la surface extérieure.
PCT/JP2004/016375 2004-10-28 2004-10-28 Papier pour impression à jet d’encre WO2006046312A1 (fr)

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PCT/JP2004/016375 WO2006046312A1 (fr) 2004-10-28 2004-10-28 Papier pour impression à jet d’encre
EP05107398A EP1658994A1 (fr) 2004-10-28 2005-08-11 Feuille pour l'enregistrement à jet d'encre
CN200510092314.XA CN1769065A (zh) 2004-10-28 2005-08-26 喷墨记录片材

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US20060210729A1 (en) * 2005-03-18 2006-09-21 Konica Minolta Photo Imaging, Inc. Ink-jet recording sheet
US8053044B2 (en) 2007-07-31 2011-11-08 Hewlett-Packard Development Company, L.P. Media for inkjet web press printing
US9067448B2 (en) * 2012-05-02 2015-06-30 Eastman Kodak Company Pre-treatment composition for inkjet printing
US8846166B2 (en) * 2012-10-09 2014-09-30 Canon Kabushiki Kaisha Recording medium
WO2017058246A1 (fr) 2015-10-02 2017-04-06 Hewlett-Packard Development Company, L.P. Compositions d'encollage
CN108136807A (zh) 2015-11-06 2018-06-08 惠普发展公司，有限责任合伙企业 可印刷记录介质

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JP2000351267A (ja) * 1999-06-11 2000-12-19 Asahi Glass Co Ltd 顔料インク用記録媒体および記録方法
JP2001287451A (ja) * 2000-01-31 2001-10-16 Nippon Paper Industries Co Ltd 顔料インクに好適なインクジェット記録媒体
JP2001328340A (ja) * 2000-05-19 2001-11-27 Fuji Photo Film Co Ltd インクジェット記録用シート
JP2002160442A (ja) * 2000-11-27 2002-06-04 Konica Corp インクジェット記録用紙
JP2004114459A (ja) * 2002-09-25 2004-04-15 Mitsubishi Paper Mills Ltd インクジェット記録方法

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JP2750433B2 (ja) 1988-02-12 1998-05-13 日本合成化学工業株式会社 インクジェット記録用紙
JPH07285265A (ja) 1994-04-18 1995-10-31 Sekisui Chem Co Ltd 水性インク用記録材
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JP2000351267A (ja) * 1999-06-11 2000-12-19 Asahi Glass Co Ltd 顔料インク用記録媒体および記録方法
JP2001287451A (ja) * 2000-01-31 2001-10-16 Nippon Paper Industries Co Ltd 顔料インクに好適なインクジェット記録媒体
JP2001328340A (ja) * 2000-05-19 2001-11-27 Fuji Photo Film Co Ltd インクジェット記録用シート
JP2002160442A (ja) * 2000-11-27 2002-06-04 Konica Corp インクジェット記録用紙
JP2004114459A (ja) * 2002-09-25 2004-04-15 Mitsubishi Paper Mills Ltd インクジェット記録方法

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